1. Field of Invention
This invention relates to a method for treating waste acid, and especially, to a method for solidifying and stabilizing waste acid. The method of the present invention can improve efficiency of the solidifying steps and stability of the solidified waste acid.
2. Related Art
In general, the radioactive-contaminated metal wastes include stainless steel and carbon steel which use in the construction of the nuclear power plant. Since of the well worn piping of the nuclear power plant has to be replaced, a large amount of the radioactive-contaminated stainless steel should be treated. Decontaminants and methods for decontaminating have been improved and are applied, such as mechanical decontaminating by hydraulic giant; electrochemical decontaminating by a mixture of phosphoric acid, sulfuric acid, and nitric acid; and chemical decontaminating by decontaminant containing fluoroboric acid. The radioactive-contaminated metal wastes can reach regulations on final disposal of low-level waste after treated by the above-mentioned methods.
Decontaminant containing phosphoric acid and fluoroboric acid are widely applied in the decontamination of the radioactive metal wastes. For example, the mixture of phosphoric acid and nitric acid is applied for decontaminating of the metal wastes containing copper and aluminum; the mixture of phosphoric acid, sulfuric acid and nitric acid is applied to electrochemical decontaminating suitable for the stainless steel wastes; and the decontaminant containing fluoroboric acid is applied to chemical decontaminating. During the decontaminating process, the metal ions accumulate in the decontaminant gradually. Then, the metal salts precipitated after reached the saturated concentration. The precipitated material in the decontaminant is disadvantageous to the decontaminating process. Moreover, if the decontaminant is contaminated by the nuclides and the radioactivity thereof raises, the decontaminant should be regenerated. Metal ions of the recycled decontaminant containing phosphoric acid and fluoroboric acid can be removed by way of oxalic acid selective precipitation, electrolysis recovery, and cation exchange, so that the decontaminant can be recovered and reused thereafter. After several times of the regenesis, decontaminant has to be eliminated since the radioactivity thereof is high. The used decontaminant becomes waste acid.
At the present day, the treatment of radioactive waste acid still makes progress. In the conventional process, the used decontaminant containing fluoroboric acid is treated by destroying the BF4− chelate therein so that CaF2 can be precipitated. BE4, which is stable in the room temperature, can be hydrolyzed to form HF by aluminum salt as the catalyst, and then CaF2 is formed after addition of calcium ion. The aforementioned reactions are the following formulas:3HBF4+Al2(SO4)3+9H2O2H3AlF6+3H3SO4+3H3BO3; andH3AlF6+3Ca(OH)23CaF2+Al(OH)3+3H2O.In the formulas, the amount of aluminum salts has to add more than the concentration of fluoroboric acid so that the efficiency of eliminating fluoroboric acid can be ensured. The conventional method for eliminating fluoroboric acid in waste acid is effective but, however, the amount of the secondary waste will increase.
The conventional methods for treating used decontaminant containing phosphoric acid include selectively precipitating and directly neutralizating. In the method of selectively precipitating, for example, in order to treat 2500 L of used decontaminant containing phosphoric acid, 117 kg of iron powder and 1558.5 kg of oxalic acid is necessary to make phosphoric acid precipitate; 7089 L of water is necessary for solid-liquid separation; and the separated water is needed to neutralize and to eliminate oxalic acid by ultraviolet and ozone. After that, the treated decontaminant has to eliminate the radioactivity further. As described in the U.S. Pat. No. 5,645,518 which is titled “Method for stabilizing low-level mixed wastes at room temperature”, the phosphate ceramic material is applied to treat the solid and liquid wastes. The solid waste is grinded to a size in a range between 4 and 75 micrometers, contacted the grinded powder with phosphate-containing solution to create phosphates of the oxide in a sol-gel, and solidified the sol-gel. The solidified waste is convenient for follow-up treatment.
As described above, the conventional methods for treating waste acid have disadvantages including: (1) a large amount of the neutralizer is necessary to mix with the same amount of waste acid so that the effect of compaction of waste acid is undesired; (2) the solid sludge and liquid waste generated during treating of waste acid have to treat by another process so that the secondary contamination and the large amount of waste are undesired; (3) heat generated during the treatment of waste acid is hard to control so that the rapid setting caused by heat is disadvantageous to waste acid; and (4) applying neutralizers separately to waste acid is adverse for stabilization of waste acid. The aforementioned disadvantages should be eliminated to improve the solidification and stabilization of waste acid.
In this regard, it is important to provide a method for solidifying and stabilizing waste acid which prevents formation of secondary contamination, has low cost, simplify the processes, and improves the efficiency of solidification to eliminate the foregoing drawbacks.